In the article the results of laboratory investigations of two versions of low-temperature synthesis for compact composite carbon - titanium carbide/titanium diboride (C – TiC/TiB2) are presented. The article concerns the preliminary examination of the thermodynamic probability of titanium carbide and titanium boride synthesis during the process of standard baking at the temperature of 1050±10ºС in the volume of carbon electrode, which composition contains boron oxide and one of the refractory metals; the synthesis taking place directly during the electrolytic reduction of the melts at the temperature of 965-970°С in the volume of carbon cathode, containing metal oxides, is also examined. After preliminary standard preparation of mixing the initial components (petroleum coke, metallic titanium Ti, titanium oxide TiO2, boron oxide B2O3 and binder), cathode samples were formed, which were calcined under a layer of petroleum coke. Experiments with different holding times during the electrolytic process showed a continuous film of aluminum on the surface of the cathode, which indicates acceptable wettability. The presence of TiC/TiB2 was confirmed by X-ray phase analysis and X-ray structural analysis (SEM-EDS analysis). Innovative technologies presented for the production of composite electrode materials could be used for the synthesis of wide range of the composite products in С – МеС/МеВ2 system. The equivalent value of petroleum coke and oxides of refractory metals allows supposing the short payback period of the use composite cathode blocks in existing pots and in pots under design.